MC-FT-NCHE312.

1-1-ENG
Requirements for this paper/Benodighede vir hierdie vraestel: Resources/Hulpmiddels:

Answer Scripts/ Multi-choice cards (A4)/

Antwoordskrifte: Multikeusekaarte (A4) Atkins' Physical Chemistry 11th
Attendance Slips (Fill-in Paper)/ Graph Paper/ Ed or Int Ed
Presensiestrokies (Invulvraestel): X GrafiekPapier X
Scrap Paper/ Calculators/
Rofwerkpapier X Sakrekenaars X
Multi-choice cards (A5)/ Laptop (Power not provided)/
Multikeusekaarte (A5) Skootrekenaar (Krag word nie voorsien nie) X

Type of Assessment/ Exam Opportunity:1 Duration/ 3 Hrs 00 Min

Tipe Assessering: Tydsduur:

Paper Number/ Maximum Marks/ 100

1
Vraestel Nommer: Maksimum Punte:

Module Code/ Module Description/

NCHE312 PHYSICAL CHEMISTRY III
Modulekode: Module Beskrywing:

Examiner(s)/ Prof RJ Kriek-PC;Dr MP Bilibana-MC;

Date/ 2022/06/14
Eksaminator(e): Datum:

Time/
Tyd:
09:00
Internal/Interne
Moderator(s): Prof PG van Zyl-PC;Prof I Bahadur-MC;
Qualification/
BSc
Kwalifikasie:
External Moderator(s)/
Eksterne Moderator(s):

ORDINARY
Submission of answer scripts/Inhandiging van antwoordskrifte:

Details of student / Besonderhede van student:

Title/ Initials/ Surname/

Titel: Voorletters: Van:
University Number/ Contact Number/
Universiteitsnommer: Kontaknommer:

Signature/
Handtekening:

Examination Instructions / Eksamenvoorskrifte

1. Students are allowed into the venue in the first half hour of a 1. Studente mag in die eerste halfuur van ‘n sessie tot die lokaal
session, but no extra time is granted. toegelaat word, maar geen ekstra tyd word toegestaan nie.
2. No student is allowed to leave the venue before half an hour of 2. Geen student word toegelaat om die lokaal te verlaat binne die
the examination session has elapsed. eerste halfuur van die eksamensessie nie.
3. Students bring bags to the venue at own risk, and must put them 3. Student bring sake na lokaal op eie risiko, en moet dit voor in die
in front of the room. lokaal neersit.
4. Students may not have cell phones/electronic devices with them 4. Studente mag nie selfone/elektroniese toestelle by hulle hê en/of
and/or handle them. hanteer nie.
5. No refreshments are allowed in the examination venue. 5. Geen verversings word in ‘n eksamenlokaal toegelaat nie.
6. Students may not leave the room for a smoke break. 6. Studente mag nie die lokaal verlaat om te gaan rook nie.
7. Write on both sides of each page. 7. Skryf op beide kante van die bladsye.
8. Write in black or blue ink only. 8. Skryf slegs in swart of blou ink.
9. No pages may be removed from the answer scripts. 9. Geen bladsye mag uit die antwoordskrif verwyder word nie.
10. Students may not have unauthorised material with them during a 10. Student mag nie ontoelaatbare materiaal by hulle hê tydens ‘n
session, e.g. notes and/or objects that contain notes. sessie nie, bv. Notas en/of objekte wat notas bevat nie.
11. No items may be borrowed during the session. 11. Geen items mag tydens die sessie geleen word nie.
12. Students may not attempt to assist another student, or attempt to 12. Studente mag nie ‘n ander student probeer help or probeer om
obtain assistance. hulp te kry nie.
13. Students must hand in their answer scripts to invigilators before 13. Studente moet hul antwoordskrifte aan toesighouers oorhandig
they leave the venue. voordat hulle die lokaal verlaat.
14. The attendance slip on the back cover that also serves as an 14. Die presensiestrokie op die agterblad, wat ook as onderneming
undertaking, must be completed and handed in. geld, moet voltooi en ingegee word.
READ THE FOLLOWING INSTRUCTIONS THOROUGHLY
• DO ONLY SECTION A OR B
• Only the prescribed text book is allowed. No additional notes or old papers are
allowed in the examination room.

• Show all your calculations. Marks cannot be awarded for steps or calculations that
are not shown.

• This is a pro forma paper.

• Answers on questions must be given in the blank spaces below each question.

• Where applicable give units for all answers.

• The back of pages can also be used, but then it should be indicated at each question. It can
also be used for own scribbling.

• Complete the paper in pen.

• Programmable calculators are allowed.

NCHE312: Paper 1 | Exam 1st opp | Full-time 1/22

SECTION A
Question A1
A pulsating star in the Crab Nebula, NP 0532, emits both radio pulses and optical pulses. A radio
pulse is observed at 196.5 MHz. Calculate (i) the corresponding wavelength (in nanometer), (ii)
the energy of the photon in J, eV and J.mol-1, and (iii) the momentum of the photon. [9]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 2/22
Question A2
Calculate the de Broglie wavelength (in pm) of an electron that has been accelerated by an
external potential of 100 V. The acquired energy of the electron can be expressed as E = qV,
where q is the charge of the electron and V the external potential. [6]

Question A3
How would you go about to determine the identity of an unknown molecule with the aid of infrared
spectroscopy? [3]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 3/22
Question A4
The H2 molecule and the HF molecule have harmonic vibrational frequencies of 1.32 x 1014 Hz
and 1.241 x 1014 Hz respectively. Calculate (a) the force constant of the H-H bond, and (b) the
force constant of the H-F bond. Comment on your answer. [5]

Question A5
A particle is moving in one dimension between x = a en x = b. The potential energy is such that
the particle cannot be outside these limits and the wave function is given by ψ = A/x.

a) Determine the normalisation constant A.

𝑥𝑥 𝑛𝑛+1
Wenk / Hint: ∫ 𝑥𝑥 𝑛𝑛 𝑑𝑑𝑑𝑑 = 𝑛𝑛+1
+ 𝑘𝑘 [5]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 4/22
b) If a = 0.5 and b = 2 show by means of a sketch where the probability would be the greatest
to encounter the particle. Also give a complete equation for the probability. [4]

Question A6
The vibration frequency of the N2 molecule, which can be approximated as being a harmonic
oscillator, corresponds to a wave number of 2360 cm-1. Calculate the zero-point energy as well
as the energy corresponding to first excited state. [6]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 5/22

Question A7
A person remarks to you that the J = 200 → J = 201 transition of the rotational spectrum of I2 can
be described precisely by the rigid rotor equations from quantum mechanics. Give two reasons
why you should question the validity of this statement. [4]

Question A8
Ammonia has two rotational constants,I∥ = 4.413 x 10-47 kg.m2 and I⊥ = 2.806 x 10-47 kg.m2.
� and B
Calculate (i) the rotational constants A �, and (ii) the value of the lowest non-zero rotational
energy. [6]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 6/22
Question A9
The rotational constant for CO is 1.9314 cm-1 and 1.6116 cm-1 in the ground and first excited
vibrational states, respectively. By how much does the internuclear distance change as a result
of this transition? [7]

Question A10
Indicate by means of a tick () which of the following molecules will absorb or emit light due to
rotational energy transitions. Indicate by means of a cross () which molecules will not do this.
Do not guess – if your answer is incorrect a mark will be deducted. [5]

Molecule /
H2
HCl
CH3Cl
CO2
SF6

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NCHE312: Paper 1 | Exam 1st opp | Full-time 7/22
Question A11
Cylinders of oxygen contain about 0.1 dm3.mol-1 gas at 25 °C.
(i) What would be the pressure of the cylinder (in bar) under these conditions based on (a) the
perfect gas equation, and (b) the van der Waals equation? [7]

(ii) Is it attracting or repulsive forces that dominate under these conditions? Motivate your
answer. [2]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 8/22
Question A12
By definition, the compressibility of an ideal gas is equal to 1. By what percentage does this value
change for (i) hydrogen, and (ii) oxygen? Give the assumptions of the conditions at which you
do these calculations. [5]

Question A13
For a Daniell cell (see the accompanying sketch) at 25°C ∆rG° = -212.7
kJ.mol-1, b(CuSO4) = 1.0 x 10-3 mol.kg-1, and b(ZnSO4) = 3.0 x 10-3 mol.kg-1.
(Take γ+ = γ- = γ± in the respective compartments.)

(i) Calculate the ionic strength of the solutions in the two compartments.
[4]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 9/22

(ii) Calculate mean ionic activity coefficients in the compartments by using the Debye Hückel
Limiting law. [4]

(iii) Calculate the reaction quotient. [3]

(iv) Calculate the standard cell potential. [2]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 10/22
(v) Calculate the cell potential. [3]

Question A14
A reaction, 2A → P, with a third-order rate equation, has a rate constant of k = 6.50 x 10-4
dm6.mol-2.s-1.
(i) Write the rate equation for this reaction. [2]

(ii) Determine the integrated rate equation from the rate equation. [4]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 11/22

(iii) How long will it take (in hours) for a concentration of 0.07 M to half? [4]

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TOTAL OF SECTION A (100)
NCHE312: Paper 1 | Exam 1st opp | Full-time 12/22
SECTION B
Question B1
On page 292 (10th edition) Atkins writes the following:

“Such total failure of classical physics for small objects implied that its basic concepts are false.
A new mechanics – quantum mechanics – had to be devised to take its place. … by supposing
that, rather than travelling along a definite path, a particle is distributed through space like a
wave.”

(i) What is the single new basic principle that quantum mechanics put forward? [1]

(ii) (a) Which equation inherently showed the above-mentioned basic principle? (b) Give this
equation. [2]

(iii) What is the energy of one mole of photons that are incident on a piece of iron metal if they
have a wavelength of 365 pm? [4]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 13/22
(iv) Within which part of the electromagnetic spectrum does an electron fall that is emitted from
the above-mentioned iron metal (φ = 4.5 eV) with a speed of 3.782 x 107 m.s-1? [4]

(v) If the speed, as given in (iii), was determined with reasonable certainty, what is the
uncertainty in the position of the electron, emitted from the iron metal, in (iv)? [3]

(vi) The above-mentioned emitted electron is absorbed by a carbon nanotube with a length of 5
nm (see below). Electromagnetic radiation with an energy of 0.165 eV excites the electron
between two consecutive energy levels. Which two energy levels are these? [6]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 14/22

Question B2
Based on your calculation or knowledge, choose only one of the options for each question. Your
calculation will not be marked; only your answer.
2.1 The second virial coefficient of ammonia, NH3, is -40.4 cm3 mol-1 at 600K. What does this
imply about the nature of the interactions between the molecules at this temperature? [2]

A The interactions between molecules are attractive.

B The interaction between molecules is negligible.
C Nothing. The value of the virial coefficient is unrelated to the molecular
interactions.
D The interactions between molecules are repulsive.

2.2 What would be the quantum mechanical zero-point energy of an electron confined within
a one-dimensional box of length 1.0 nm? [4]

A 2.4 x 10-19 J
B 0J
C 6.0 x 10-20 J
D 5.4 x 10-19 J

2.3 Which of the following statements is always true for a liquid mixture of two components A
and B in equilibrium with a mixture of their vapours? [2]

A µA(l) = µB(l) en/and µA(g) = µB(g)

B µA(l) = µA(g) = µB(l) = µB(g)
C µA(l) = µA(g) en/and µB(l) = µB(g)
D µA(l) ≠ µA(g) ≠ µB(l) ≠ µB(g)

2.4 Determine the mean activity coefficient for the ions in an aqueous solution of potassium
sulphate, K2SO4, of molality 0.010 mol kg-1 at 25 °C, by employing the Debye-Hückel
limiting law. [4]

A 0.943
B 0.666
C 0.750
D 0.690

Question B3
The movement of an electron is described by the wavefunction ψ(x) = √2 sin πx (which is already
normalised) in the range where x = 0 − 1.
(i) What is the normalisation constant of the wavefunction? [1]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 15/22
(ii) What is the probability of finding the electron in the range (a) x = 0.25 − 0.50 and (b) x =
0.35 − 0.60? [8]

(iii) Explain the difference that you observe in your answer for the two regions in (ii). [2]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 16/22
Question B4
A mass of 45 g hangs on a spring that oscillates with a frequency of 2.4 vibrations per second
with an amplitude of 4.0 cm.
(i) Calculate the force constant of the spring. [3]

(ii) If the energy of the system is considered quantum mechanically calculate the quantum
number υ. [4]

Question B5
Consider the 12C16O molecule as a rigid rotor with an internuclear distance of 1.13 Å.
(i) Calculate the effective mass for this molecule. [3]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 17/22
(ii) Now determine the moment of inertia for this molecule. [2]

(iii) Determine the energies of the two lowest energy levels (in J). [4]

(iv) Calculate the frequency of the absorbed electromagnetic radiation when the C16O
12

molecule is excited from the J = 1 level to the J = 2 level. [4]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 18/22
Question B6
It has been observed that the vibrational levels of mercury hydride (HgH) converge rapidly. The
observed vibrational intervals lie at the following values for 1 ← 0, 2 ← 1, …, respectively (in cm-
1
): 1203.7, 965.6, 632.4, and 172. Determine the bond strength (in Joule) of a single molecule
by employing a Birge-Sponer plot. Construct a physical graph using the supplied graph paper.
[8]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 19/22
Question B7
NH3(g) is heated from 25°C to 500°C. Calculate the molar enthalpy of formation for NH3(g), as
a real gas, for this heating process. [9]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 20/22
Question B8
The density of N2 is experimentally determined as being 544 g.L-1 at 180 bar and -123.15 °C.
(i) Calculate the value of the molar volume, Vm. [4]

(ii) Calculate the value of the compression factor, Z, at -123.15 °C. [4]

(iii) What can you deduct from the value of Z? [3]

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NCHE312: Paper 1 | Exam 1st opp | Full-time 21/22
Question B9
Nitrogen is a gas that can be liquefied, by employing the Joule-Thomson effect, and is used for
cooling.
(i) Calculate the isothermal Joule-Thomson coefficient for nitrogen by employing the
appropriate data for nitrogen in the tables. [4]

(ii) Now determine the energy (in kJ) that must be supplied as heat, to maintain constant
temperature, when 20 mol of nitrogen expands in an isothermal Joule-Thomson experiment
as a result of a pressure drop of 67 atm. [5]

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TOTAL OF SECTION B (100)
File reference: 8.1.7.2.2
NCHE312: Paper 1 | Exam 1st opp | Full-time 22/22